General electron theory of reduction and oxidation of metals

The significance of the new theory of metal reduction from ores has been demonstrated. It was shown that all the existing versions of the theory are based on atomic-molecular representations of the early 20-th century where reduction is considered as a process of exchange of oxygen atoms between a reducing agent and oxide molecules. These representations do not take into account changes in the crystalline structure of oxides and in the state of a gas medium with change in temperature and pressure. The attention here was drawn to the absence of molecules in oxides, and atoms in metals. Inconsistency of a number of the theory conclusions with practice of reduction during operation of plants was revealed. Based on the assumptions of redox reactions as processes of exchange of reagents by the valence electrons, defective ionic structure of real crystals, changes in the state of the gaseous medium during heating and pressure increase using some statements of quantum mechanics on the distribution of electrons in solids, the authors have developed electron version of the reduction theory. This theory is based on the unity of the anionic sublattice of all crystals of the oxide phase and the collective electronic system of all valence electrons of metal cations in oxide. It is shown that in the reduction plants, due to the thermal ionization of gases and thermionic emission from the surface of the heated bodies, the gas medium is plasma. The presence of charged particles in the plasma ensures their interaction at a considerable distance and the course of chemical processes in the kinetic mode. The gaseous reduction products are removed from the reaction zone with exhaust gases, and the electrons released in the plasma are absorbed by the oxide surface and exist in the oxide together with the anionic vacancies that arise when oxygen is removed. In high-grade ores the vacancies merge and disappear on the oxide surface, and the free electrons of the vacancies combine the nearest cations with a metal bond to form a metal shell which later turns into carbides. The formation of carbide shells blocks the oxide surface and stops reduction. When temperature rises and the shells melt the reduction process resumes. Therefore, the carbon-thermal reduction produces cast iron and high-carbon ferroalloys. In low-grade and complex ores the vacancies are scattered in the oxide volume along the total anionic sublattice forming solution of vacancies and free electrons. The vacancies merge and disappear in places of increased concentration of cations where the Fermi level of atoms is less than the chemical potential of the free electrons. In the formed anionic void the free electrons rearrange metal cations with low Fermi energy and bind them with a metal bond bypassing the stage of atom formation. Crystal growth in an anionic void occurs without resistance from the parent oxide phase.

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